Transition-metal-catalyzed carbonylation reactions of olefins and alkynes: a personal account.
Transition-metal-catalyzed carbonylation reactions of olefins and alkynes: a personal account.
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DOI：
10.1021/ar400222k
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发表时间：
2014-02
影响因子：
18.3
通讯作者：
Xiao‐Feng Wu;Xianjie Fang;Lipeng Wu;R. Jackstell;H. Neumann;M. Beller
中科院分区：
文献类型：
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作者：
Xiao‐Feng Wu;Xianjie Fang;Lipeng Wu;R. Jackstell;H. Neumann;M. Beller
一氧化碳于 18 世纪被发现并被识别。自 80 年前首次在工业中应用以来，学术和工业实验室已广泛探索二氧化碳在化学反应中的应用。如今，有机化学家在有机化学中通常使用二氧化碳来合成各种羰基化合物。尽管取得了所有这些成就和一个世纪的羰基化催化，但许多重要的研究问题和挑战仍然存在。值得注意的是，除了学术发展之外，工业界也大规模应用二氧化碳的羰基化反应。事实上，当今均相催化（就规模而言）最大的应用是羰基化反应，尤其是加氢甲酰化。此外，绝大多数乙酸是通过甲醇的羰基化（孟山都或卡蒂瓦工艺）生产的。烯烃/炔烃与亲核试剂（例如醇和胺）的羰基化代表了此类反应的另一种重要类型。在本报告中，我们讨论了我们在不饱和化合物的各种羰基化和相关反应方面的工作。铑催化的内烯烃异构化和加氢甲酰化反应可以直接获得更高价值的醛。催化氢氨甲基化提供了直接合成取代胺甚至杂环的理想方法。最近，我们的团队还开发了基于铱、钌和铁的所谓替代金属催化剂。羰基化反应的未来如何？ CO 已经是有机合成中最通用的 C1 结构单元之一，并广泛应用于工业中。然而，由于二氧化碳的高毒性和气态性质，有机化学家通常不愿意更频繁地应用羰基化。此外，最近的新规定使一氧化碳的运输变得更加困难。因此，研究人员需要开发并更频繁地使用实用且良性的二氧化碳生成试剂。除了甲酸盐、醇和羰基金属之外，二氧化碳也提供了有趣的选择。工业化学家寻求易于制备的催化剂和无专利的配体/配合物。此外，非贵金属配合物也会引起学术和工业研究人员的兴趣。甲基丙烯酸甲酯的新型有机玻璃工艺是改进催化剂的一个重要例子。该反应使用了特定的钯/双膦催化剂，从而导致该技术的成功实施。用于低反应性烯烃的相关羰基化的活性更高、生产率更高的催化剂将允许该方法的其他大规模应用。从学术角度来看，研究人员继续寻找与更多官能化烯烃的选择性反应。最后，由于简单金属羰基配合物的挥发性，羰基化反应今天仍然是均相催化领域。发明更稳定和可回收的多相催化剂或无金属羰基化（自由基羰基化）将很困难，但可能为年轻化学家带来有趣的挑战。
Carbon monoxide was discovered and identified in the 18th century. Since the first applications in industry 80 years ago, academic and industrial laboratories have broadly explored CO's use in chemical reactions. Today organic chemists routinely employ CO in organic chemistry to synthesize all kinds of carbonyl compounds. Despite all these achievements and a century of carbonylation catalysis, many important research questions and challenges remain. Notably, apart from academic developments, industry applies carbonylation reactions with CO on bulk scale. In fact, today the largest applications of homogeneous catalysis (regarding scale) are carbonylation reactions, especially hydroformylations. In addition, the vast majority of acetic acid is produced via carbonylation of methanol (Monsanto or Cativa process). The carbonylation of olefins/alkynes with nucleophiles, such as alcohols and amines, represent another important type of such reactions. In this Account, we discuss our work on various carbonylations of unsaturated compounds and related reactions. Rhodium-catalyzed isomerization and hydroformylation reactions of internal olefins provide straightforward access to higher value aldehydes. Catalytic hydroaminomethylations offer an ideal way to synthesize substituted amines and even heterocycles directly. More recently, our group has also developed so-called alternative metal catalysts based on iridium, ruthenium, and iron. What about the future of carbonylation reactions? CO is already one of the most versatile C1 building blocks for organic synthesis and is widely used in industry. However, because of CO's high toxicity and gaseous nature, organic chemists are often reluctant to apply carbonylations more frequently. In addition, new regulations have recently made the transportation of carbon monoxide more difficult. Hence, researchers will need to develop and more frequently use practical and benign CO-generating reagents. Apart from formates, alcohols, and metal carbonyls, carbon dioxide also offers interesting options. Industrial chemists seek easy to prepare catalysts and patent-free ligands/complexes. In addition, non-noble metal complexes will interest both academic and industrial researchers. The novel Lucite process for methyl methacrylate is an important example of an improved catalyst. This reaction makes use of a specific palladium/bisphosphine catalyst, which led to the successful implementation of the technology. More active and productive catalysts for related carbonylations of less reactive olefins would allow for other large scale applications of this methodology. From an academic point of view, researchers continue to look for selective reactions with more functionalized olefins. Finally, because of the volatility of simple metal carbonyl complexes, carbonylation reactions today remain a domain of homogeneous catalysis. The invention of more stable and recyclable heterogeneous catalysts or metal-free carbonylations (radical carbonylations) will be difficult, but could offer interesting challenges for young chemists.